CN103834061B - Low-quality vegetable and animals oils modification and degree of depth epoxidation prepare the method for environment-friendlyplasticizer plasticizer - Google Patents
Low-quality vegetable and animals oils modification and degree of depth epoxidation prepare the method for environment-friendlyplasticizer plasticizer Download PDFInfo
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- 238000010992 reflux Methods 0.000 claims description 10
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- 239000003054 catalyst Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 14
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
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- Fats And Perfumes (AREA)
- Epoxy Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of method that low-quality vegetable and animals oils modification and degree of depth epoxidation prepare environment-friendlyplasticizer plasticizer, the present invention is with sewer oil, hogwash fat, oil pressing factory's low-quality animal-plant oil of old wet goods for raw material, and oxirane value is high, environment-friendly epoxy fatty acid ester plasticiser to adopt substep esterification → epoxidised processing method of introducing double bond → degree of depth to prepare.The epoxy plasticizer productive rate utilizing the present invention to prepare is high, cost is low, oxirane value high (> 5.0%), resistance to migration is good, with polyvinyl chloride (PVC) RESINS, there is good consistency and high plasticizing efficiency, alternative or Some substitute phthalic ester plasticizer is used for the manufacture of artificial polyvinyl chloride leather, footwear material, outdoor decoration material, sports goods, PVC, electric wire etc., and application prospect is extensive.
Description
Technical field
The present invention relates to a kind of method that low-quality vegetable and animals oils modification and degree of depth epoxidation prepare environment-friendly plasticizer, belong to utilization of waste as resource field.
Background technology
Softening agent is the maximum class chemical of output in polyvinyl chloride (PVC) goods used additives, consumption, its global annual requirement is now more than 8,000,000 tons, and along with the rise of 21 century Material Field " to mould Dai Gang ", " to mould Dai Mu " theory, estimate that following 20 years internal plasticizer industries will grow continuously and fast with the speed of about 10%.Phthalic ester is the class softening agent that current consumption is maximum, use range is the widest, accounts for 95% of the total consumption of global softening agent.But increasing research report is pointed out, phthalic ester plays the effect of similar female hormone in vivo, can disturbance endocrine, man semen amount and sperm quantity are reduced, Sperm Motility reduces, sperm morphology is abnormal, is cause man (especially boy) reproductive problems " arch-criminal ".In addition, National Cancer Institute has carried out biological assay to the carinogenicity of phthalic ester, and its conclusion is: this kind of softening agent is the carcinogens of rat and mouse, and a large amount of absorption can make the liver of rodent carcinogenic.In view of genotoxicity and the carinogenicity of phthalic ester, European Union, united states, japan and other countries man this kind of softening agent of clear stipulaties can not be used for toy for children, food product pack, medicine equipment etc. with the goods of human body close contact, China has also in succession put into effect the use of numerous statutory standard to phthalic ester plasticizer and has limited, and PVC plastic industry is in the urgent need to the environment-friend substitution product of this series products.
Epoxy aliphatic ester class softening agent is a class environment-friendly plasticizer of comparatively maturation, large usage quantity at present, there is the advantages such as nontoxic, heat-resisting, photostabilization is good compared with traditional phthalic ester, while plasticized PVC plastics, also have the effect of stablizer concurrently, be permitted for food and medical packaging material in many countries.But high-quality epoxy plasticizer in the market mostly adopts expensive crude vegetal (as soybean oil, linseed oil, vegetable seed wet goods) to be raw material, and production cost is higher, limits the range of application of product; The every annual meeting of China produces the sewer oil of 7,000,000 tons, swill wet goods, its main component is also natural animal-plant grease, but character there occurs change in use, recovery, storage, also can produce some toxic substances, sewer oil carries out selling restaurant, restaurant as edible oil after simple deodorization and discoloration by some bad retailers, and sewer oil returns to the healthy of dining table serious harm eater.The recycling one of current sewer oil, swill wet goods is as production biodiesel raw material, but China's this respect progress is slow; Two is be used as softening agent by modification, but traditional method of modifying many employings sewer oil/hogwash fat → methyl alcohol transesterify → epoxidised operational path, but the sewer oil/swill wet goods low quality reclaimed, show as acid number high, iodine number is low.During free fatty acid content height, have a strong impact on follow-up transesterification reaction and epoxidation reaction, run off more in washing sepn process and affect yield; Cannot degree of depth epoxidation (epoxidation reaction mainly occurs in double bond) when iodine number is low, product oxirane value is low, poor as softening agent resistance to migration, therefore how to utilize to high added value these low-quality vegetable and animals oils extremely urgent.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and provide a kind of low-quality vegetable and animals oils modification and degree of depth epoxidation to prepare the method for environment-friendly plasticizer, the method with low-quality vegetable and animals oils cheap and easy to get for raw material, by substep esterification, introduce double bond, degree of depth epoxidation technology substantially increases the oxirane value of product, fundamentally solve the resistance to migration problem of epoxy plasticiser, quality product excellence is stable, at artificial polyvinyl chloride leather, polyvinyl chloride shoe material, outdoor decoration material, sports goods, PVC, the manufacture fields such as electric wire show wide application prospect.
For achieving the above object, technical scheme of the present invention comprises the following steps, wherein raw materials used in mass fraction:
(1) pre-treatment: sedimentation after low-quality vegetable and animals oils 100 parts is warming up to 40 ~ 60 DEG C, filtration, removing solid impurity, the phosphoric acid of oil plant weight 0.2 ~ 0.4% and the water of oil plant weight 2 ~ 5% is added again in the oil plant after removal of impurities, continue to stir at 40 ~ 60 DEG C to come unstuck, finally gained oil plant is dewatered in 0.1atm underpressure distillation;
(2) esterification: pretreated oil plant 100 parts, methyl alcohol 1 ~ 3 part, the vitriol oil 0.5 ~ 1.0 part are mixed, esterification 2 ~ 3 hours under 70 ~ 80 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally at 70 DEG C, distillation dehydration under 0.1atm condition;
(3) transesterify: the oil plant after esterification 100 parts, unsaturated alcohol 4 ~ 6 parts, alkaline catalysts 0.5 ~ 1.5 part mix, transesterify 2 ~ 3 hours under 55 ~ 65 DEG C of conditions, after completion of the reaction, by product washing, stratification, upper strata oil plant distillation dehydration under 0.1atm, 70 DEG C of conditions is got;
(4) epoxidation: get 6 ~ 8 parts, the hydrogen peroxide of 35%, 0.8 ~ 1.2 part, active oxygen carrier, acid catalyst 0.1 ~ 0.5 part, stablizer 0.05 ~ 0.1 part mix, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction 60 ~ 65 DEG C, time for adding controls in 1 ~ 2 hour, dropwise and continue insulated and stirred reaction 4 ~ 8 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, in 70 DEG C, underpressure distillation dehydration under 0.1atm condition, obtains epoxy aliphatic ester class softening agent.
Further setting to be described low-quality vegetable and animals oils be in sewer oil, hogwash fat, the old oil in oil pressing factory one or more.
Further setting to be the unsaturated alcohol in described step (3) be in vinylcarbinol, butenol, senecioate-hydroxy methacrylate, senecioate-hydroxypropyl acrylate one or more.
Further setting to be the alkaline catalysts in described step (3) be in sodium methylate, potassium hydroxide, sodium hydroxide one or more.
Further setting to be the active oxygen carrier in described step (4) be in formic acid, acetic acid one or more.
Further setting is that acid catalyst is one or more in the vitriol oil, Phenylsulfonic acid, phosphoric acid in described step (4).
Further setting to be the stablizer in described step (4) be in urea, water glass one or more.
Processing method of the present invention is high for low-quality vegetable and animals oils acid number, iodine number is low causes transesterify and epoxidation reaction degree is low, product yield is low, product oxirane value is low feature, proposes brand-new substep esterification → epoxidised operational path of introducing double bond → degree of depth.So-called substep esterification-i.e. first methanol esterification, after carry out the secondary esterification of special esters exchange.The advantage of the method is first esterification, effectively can reduce acid number, reduces the impact of acid number on follow-up transesterification reaction and epoxidation reaction; Simultaneously in rear ester-exchange reaction, introduce extra double bond by unsaturated alcohols, increase the active site of epoxidation reaction, for degree of depth epoxidation creates conditions.
Processing method of the present invention is that the high added value achieving waste is recycled, and reduce the production cost of conventional epoxy softening agent, its key problem in technology is with the old wet goods in sewer oil, hogwash fat and/or oil pressing factory for material modification prepares epoxy plasticizer:
First, substep esterification targetedly by oil plant due to become sour produce free fatty acids change into fatty acid methyl ester, both the high impact on follow-up transesterify and epoxidation reaction of acid number had been reduced, substantially increase again the yield of product, compared with removing free fatty acids method with traditional alkali cleaning, have more Atom economy;
Second, in Exchange Ester Process, no longer adopt methyl alcohol as transesterify reagent, the substitute is the alcohols in return reagent containing unsaturated double-bond, while transesterify, introduce extra double bond, add the active site of epoxidation reaction, for degree of depth epoxidation creates conditions.
3rd, in last key link of the present invention, adopt the efficient vitriol oil, Phenylsulfonic acid or phosphoric acid does catalyst catalytic epoxidation, the reaction times is shorter compared with traditional organic acid autocatalysis system, and by product is few, and product colour is light, quality is better; In addition, the present invention adopts tripoly phosphate sodium STPP that the fictitious hosts such as cheap urea, water glass are more expensive as stabilizing agent, in epoxidation process, effectively prevent the decomposition of peroxy acid and heat, the acid catalysis ring-opening reaction of epoxide, significantly improve oxirane value (>=5.5%) and the integrated quality thereof of product.
Compared with other technologies, the present invention with it difference is embodied in:
1, apply for notification number be CN101372539B application discloses a kind of method utilizing waste oil and oil foot production environment-friendlyplasticizer plasticizer, the method that this invention adopts esterification, transesterify is carried out simultaneously prepares epoxy aliphatic acid methyl ester, but esterification and transesterification reaction mechanism difference are large, catalyzer specificity is strong, and the yield of intermediate fatty acid methyl esters is not high; Secondly, at epoxidation stage, this invention adopts formic acid autocatalysis epoxidation reaction, and do not use the catalyzer such as efficient mineral acid and stablizer, the epoxidation time is long, and product oxirane value is low.
2, apply for that notification number is that a kind of waste grease that utilizes that application discloses of CN100590188C produces the method for epoxy plasticizer, this invention directly use sodium hydroxide by the lipid acid in stock oil and removing, the Atom economy of processing method is not strong, and the yield of product is low; In addition, at epoxidation stage, this invention adopts formic acid autocatalysis epoxidation equally, does not use efficient inorganic acid catalyst and stablizer, and the epoxidation time is long, and product oxirane value is not high; Finally, this invention also requires to use high efficient mixed reactor to promote speed of response at epoxidation stage, high to equipment requirements.
3, apply for notification number be CN100580025C application discloses a kind of method that sewer oil and waste oils and fats prepare epoxy plasticizer, the method adopts esterification and the transesterify of porous support solid acid and catalyzed by solid base stock oil respectively, although there is the advantage in separation, but reaction system is heterogeneous, the contact area of catalyzer and reactant is limited, catalytic efficiency is on the low side, and the cost of solid catalyst is higher; In addition, this invention requires that in esterification process methyl alcohol passes into reactor with gas phase, requires higher to conversion unit; At epoxidation stage, this invention adopts formic acid autocatalysis epoxidized fatty acid methyl esters equally, do not use efficient inorganic acid catalyst, the oxirane value of product is not high, long reaction time, although have employed tripoly phosphate sodium STPP is stablizer, price be urea, nearly 10 times of water glass stablizer, have impact on the cost of product.
Finally, above three technology all adopts single stage method at epoxidation stage, directly add in fatty acid methyl ester oil plant by peroxy acid carrier, hydrogen peroxide, although this method technique is simple, easy handling, but epoxidation process is wayward, defects such as there is the epoxidation time long, by product is many, product oxirane value is not high, color is comparatively dark, thermostability is bad.The more important thing is above-mentioned three technology all do not solve low-quality vegetable and animals oils iodine number low, cannot the epoxidised technological deficiency of the degree of depth, prepared softening agent resistance to migration is poor.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
embodiment 1
(1) pre-treatment: sedimentation after recovery sewer oil 100 parts is warming up to 40 DEG C, filtration, removing solid impurity, then add the phosphoric acid of 0.2% of oil plant weight and the water of 2%, continue to stir at 40 DEG C to come unstuck 30 minutes, finally gained oil plant is dewatered in 0.1atm underpressure distillation;
(2) esterification: pretreated oil plant 100 parts, methyl alcohol 1 part, the vitriol oil 0.5 part are mixed, esterification 3 hours under 70 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally distillation dehydration under 0.1atm;
(3) transesterify: the oil plant after esterification 100 parts, vinylcarbinol 4 parts, sodium methylate 0.5 part mix, 55 DEG C, transesterify 3 hours under reflux conditions, after completion of the reaction, washes product, stratification, gets upper strata oil plant decompression dehydration under 0.1atm;
(4) epoxidation: get 6 parts, the hydrogen peroxide of 35%, anhydrous formic acid 0.8 part, vitriol oil acid 0.1 part, 0.05 part, urea mixes, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction controls at 60 DEG C, time for adding controls in 1-2 hour, dropwise continuation insulated and stirred and react 4 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, and under 0.1atm, underpressure distillation dehydration, obtains epoxy aliphatic ester class softening agent.
Through measuring, product oxirane value reaches 6.2%.Toxicity test shows that the LD50 value of product is greater than 18g/kg, and cytotoxicity grade is less than 1 grade, therefore product can be considered safety non-toxic.Plasticising experiment shows, plasticizer consumption: when PVC consumption is 1:1 (weight ratio), can make the second-order transition temperature of PVC be reduced to-48 DEG C from 87 DEG C, and its consistency is suitable with DOP, and plasticizing efficiency is 102% of DOP; Resistance to migration experiment shows, 10 days its rate of weight loss (mobility) < 0.86%.
embodiment 2
(1) pre-treatment: sedimentation after recovery hogwash fat 100 parts is warming up to 60 DEG C, filtration, removing solid impurity, the phosphoric acid of 0.4% of oil plant weight and the water of 5% is added again in the oil plant after removal of impurities, continue to stir at 60 DEG C to come unstuck 30 minutes, finally gained oil plant is dewatered in 0.1atm underpressure distillation;
(2) methanol esterification: pretreated oil plant 100 parts, methyl alcohol 3 parts, the vitriol oil 1.0 parts are mixed, esterification 2 hours under 80 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally distillation dehydration under 0.1atm;
(3) transesterify: the oil plant after esterification 100 parts, senecioate-hydroxy methacrylate 6 parts, potassium hydroxide 1.5 mix, 65 DEG C, transesterify 2 hours under reflux conditions, after completion of the reaction, by product washing, stratification, upper strata oil plant decompression dehydration under 0.1atm is got;
(4) epoxidation: get 8 parts, the hydrogen peroxide of 35%, anhydrous formic acid 1.2 parts, Phenylsulfonic acid 0.5 part, water glass 0.1 part mix, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction controls at 65 DEG C, time for adding controls in 2 hours, dropwise continuation insulated and stirred and react 5 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, and under 0.1atm, underpressure distillation dehydration, obtains epoxy aliphatic ester class softening agent.
Through measuring, product oxirane value reaches 6.0%.Toxicity test shows that the LD50 value of product is greater than 21g/kg, and cytotoxicity grade is less than 1 grade, therefore product can be considered safety non-toxic.Plasticising experiment shows, plasticizer consumption: when PVC consumption is 1:1 (weight ratio), can make the second-order transition temperature of PVC be reduced to-45.6 DEG C from 87 DEG C, and its consistency is suitable with DOP, and plasticizing efficiency is 98.8% of DOP; Resistance to migration experiment shows, 10 days its rate of weight loss (mobility) < 1.0%.
embodiment 3
(1) pre-treatment: sedimentation after being warming up to 50 DEG C by each to sewer oil, the old oil in oil pressing factory 50 parts, filtration, removing solid impurity, the phosphoric acid of 0.3% of oil plant weight and the water of 3% is added again in the oil plant after removal of impurities, continue to stir at 50 DEG C to come unstuck 30 minutes, finally the underpressure distillation of gained oil plant is dewatered;
(2) esterification: pretreated oil plant 100 parts, methyl alcohol 2 parts, the vitriol oil 0.8 part are mixed, esterification 2.5 hours under 75 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally distillation dehydration under 0.1atm;
(3) transesterify: the oil plant after esterification 100 parts, butenol 5 parts, sodium hydroxide 1.0 mix, 60 DEG C, transesterify 2.5 hours under reflux conditions, after completion of the reaction, washes product, stratification, gets upper strata oil plant decompression dehydration under 0.1atm;
(4) epoxidation: get 7 parts, the hydrogen peroxide of 35%, anhydrous formic acid 1.0 parts, phosphoric acid 0.3 part, 0.07 part, urea mixes, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction 62 DEG C, time for adding controls in 1.5 hours, dropwise continuation insulated and stirred and react 8 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, and under 0.1atm, underpressure distillation dehydration, obtains epoxy aliphatic ester class softening agent.
Through measuring, product oxirane value is about 5.8%; Toxicity test shows that the LD50 value of product is for 20g/kg, and cytotoxicity grade is less than 1 grade, therefore product can be considered safety and environmental protection.Plasticising experiment shows, plasticizer consumption: when PVC consumption is 1:1 (weight ratio), can make the second-order transition temperature of PVC be reduced to-42 DEG C from 87 DEG C, and its consistency is suitable with DOP, and plasticizing efficiency is 97.5% of DOP; Resistance to migration experiment shows, 10 days its rate of weight loss (mobility) < 1.5%.
embodiment 4
(1) pre-treatment: sedimentation after hogwash fat 60 parts, sewer oil 40 parts are warming up to 60 DEG C, filtration, removing solid impurity, the phosphoric acid of 0.35% of oil plant weight and the water of 3% is added again in the oil plant after removal of impurities, continue to stir at 55 DEG C to come unstuck 30 minutes, finally the underpressure distillation of gained oil plant is dewatered;
(2) esterification: pretreated oil plant 100 parts, methyl alcohol 3 parts, the vitriol oil 0.6 part are mixed, esterification 2.5 hours under 70 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally distillation dehydration under 0.1atm;
(3) transesterify: the oil plant after esterification 100 parts, senecioate-hydroxypropyl acrylate 6 parts, sodium methylate 1.5 parts mix, 60 DEG C, transesterify 3 hours under reflux conditions, after completion of the reaction, by product washing, stratification, upper strata oil plant decompression dehydration under 0.1atm is got;
(4) epoxidation: get 8 parts, the hydrogen peroxide of 35%, anhydrous acetic acid 1.0 parts, Phenylsulfonic acid 0.4 part, 0.1 part, urea mixes, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction 65 DEG C, time for adding controls in 1.5 hours, dropwise continuation insulated and stirred and react 5 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, and under 0.1atm, underpressure distillation dehydration, obtains epoxy aliphatic ester class softening agent.
Through measuring, product oxirane value reaches 5.65%.Toxicity test shows that the LD50 value of product is greater than 18g/kg, and cytotoxicity grade is less than 1 grade, therefore product can be considered safety non-toxic.Plasticising experiment shows, plasticizer consumption: when PVC consumption is 1:1 (weight ratio), can make the second-order transition temperature of PVC be reduced to-44 DEG C from 87 DEG C, and its consistency is suitable with DOP, and plasticizing efficiency is 99.5% of DOP; Resistance to migration experiment shows, 10 days its rate of weight loss (mobility) < 1.1%.
Claims (7)
1. low-quality vegetable and animals oils modification and degree of depth epoxidation prepare a method for environment-friendlyplasticizer plasticizer, it is characterized in that comprising the following steps, wherein raw materials used in mass fraction:
(1) pre-treatment: sedimentation after low-quality vegetable and animals oils 100 parts is warming up to 40 ~ 60 DEG C, filtration, removing solid impurity, the phosphoric acid of oil plant weight 0.2 ~ 0.4% and the water of oil plant weight 2 ~ 5% is added again in the oil plant after removal of impurities, continue to stir at 40 ~ 60 DEG C to come unstuck, finally gained oil plant is dewatered in 0.1atm underpressure distillation;
(2) esterification: pretreated oil plant 100 parts, methyl alcohol 1 ~ 3 part, the vitriol oil 0.5 ~ 1.0 part are mixed, esterification 2 ~ 3 hours under 70 ~ 80 DEG C of reflux conditionss, the oil plant concentration after esterification is the NaHCO of 5%
3solution is washed till neutrality, finally at 70 DEG C, distillation dehydration under 0.1atm condition;
(3) transesterify: the oil plant after esterification 100 parts, unsaturated alcohol 4 ~ 6 parts, alkaline catalysts 0.5 ~ 1.5 part mix, transesterify 2 ~ 3 hours under 55 ~ 65 DEG C of conditions, after completion of the reaction, by product washing, stratification, upper strata oil plant distillation dehydration under 0.1atm, 70 DEG C of conditions is got;
(4) epoxidation: get 6 ~ 8 parts, the hydrogen peroxide of 35%, 0.8 ~ 1.2 part, active oxygen carrier, acid catalyst 0.1 ~ 0.5 part, stablizer 0.05 ~ 0.1 part mix, obtained active peroxy acid, dropping mode is adopted to be added dropwise in 100 parts of oil plants prepared through transesterify again, temperature of reaction 60 ~ 65 DEG C, time for adding controls in 1 ~ 2 hour, dropwise and continue insulated and stirred reaction 4 ~ 8 hours, after reaction terminates, point sub-cloud sour water, is the NaHCO of 5% by upper strata product concentration
3solution is washed till neutrality, in 70 DEG C, underpressure distillation dehydration under 0.1atm condition, obtains epoxy aliphatic ester class softening agent.
2. a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation prepare the method for environment-friendlyplasticizer plasticizer, it is characterized in that: described low-quality vegetable and animals oils is one or more in sewer oil, hogwash fat, the old oil in oil pressing factory.
3. prepare the method for environment-friendlyplasticizer plasticizer according to a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation, it is characterized in that: the unsaturated alcohol in described step (3) is one or more in vinylcarbinol, butenol, senecioate-hydroxy methacrylate, senecioate-hydroxypropyl acrylate.
4. prepare the method for environment-friendlyplasticizer plasticizer according to a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation, it is characterized in that: the alkaline catalysts in described step (3) is one or more in sodium methylate, potassium hydroxide, sodium hydroxide.
5. prepare the method for environment-friendlyplasticizer plasticizer according to a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation, it is characterized in that: the active oxygen carrier in described step (4) is one or more in formic acid, acetic acid.
6. prepare the method for environment-friendlyplasticizer plasticizer according to a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation, it is characterized in that: in described step (4), acid catalyst is one or more in the vitriol oil, Phenylsulfonic acid, phosphoric acid.
7. prepare the method for environment-friendlyplasticizer plasticizer according to a kind of low-quality vegetable and animals oils modification according to claim 1 and degree of depth epoxidation, it is characterized in that: the stablizer in described step (4) is one or more in urea, water glass.
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| CN107354010A (en) * | 2017-08-02 | 2017-11-17 | 合肥万之景门窗有限公司 | A kind of preparation method of plasticizer for plastic-steel door and window |
| CN108753467A (en) * | 2018-04-15 | 2018-11-06 | 桂林理工大学 | Using gutter oil as the method for raw material coproduction solid alcohol and epoxy gutter oil |
| CN109369574A (en) * | 2018-09-14 | 2019-02-22 | 许昌鑫瑞德化工科技有限公司 | A kind of processing method of modified vegetable and animals oils |
| CN109055019A (en) * | 2018-09-18 | 2018-12-21 | 重庆工商大学 | The method that chemical modification waste cooking oil prepares lube base oil |
| CN112745988B (en) * | 2019-10-31 | 2022-06-07 | 中国石油化工股份有限公司 | Modified environment-friendly plasticizer and synthetic method thereof |
| CN112812457A (en) * | 2019-11-15 | 2021-05-18 | 海安南京大学高新技术研究院 | Preparation method of modified gutter oil plasticized PVC |
| CN111925606A (en) * | 2020-07-30 | 2020-11-13 | 宜兴市鸿韵塑料有限公司 | Cold-resistant flame-retardant PVC cable sheath material |
| CN112759866B (en) * | 2021-03-01 | 2022-01-25 | 四川大学 | Method for preparing migration-resistant bio-based plasticizer by continuously increasing ester of kitchen recovered oil |
| CN113355071B (en) * | 2021-06-15 | 2023-03-21 | 长江大学 | Degradable high-strength resin water shutoff agent and preparation method and application thereof |
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